铜铅锌铁主要硫化氧化矿物浮选的基础理论研究.doc

铜铅锌铁主要硫化氧化矿物浮选的基础理论研究 【摘要】 本文针对铜铅锌铁典型的硫化矿黄铜矿、方铅矿、闪锌矿、黄铁矿、铜铅锌典型的碳酸盐矿物孔雀石、白铅矿和菱锌矿和铁氧化矿物磁铁矿、赤铁矿和褐铁矿利用4种黄药类捕收剂乙基黄药、丁基黄药、辛基黄药和十二烷基黄药、乙硫氮、丁基铵黑药、2种胺类捕收剂十二烷基胺和十八烷基胺、十二烷基硫酸钠、十二烷基磺酸钠、油酸和非离子型异丙乙硫氨酯展开了浮选纯矿物研究,并对12种捕收剂分别与10种试验矿物未活化作用后进行了FTIR研究。在总结前人研究的基础上提出了应用分子力学的方法对12种捕收剂分别与9种试验矿物作用进行了模拟和计算。根据浮选试验、红外测试结果,应用分子力学模拟和计算的捕收剂与矿物表面作用的模型和能量进行了分析,指出捕收剂与矿物表面作用的分子力学能量分析方法是可以解释捕收剂-矿物体系的相互作用。经过系列的浮选试验研究,认为试验的药剂不存在传统意义的硫化矿捕收剂和氧化矿捕收剂。其中油酸是所有试验矿物的捕收剂,不管矿物是铜铅锌铁硫化矿物、铜铅锌碳酸盐矿物还是铁氧化矿物；高级黄药是试验的硫化矿物和铜铅锌碳酸盐矿物的高效捕收剂；胺类捕收剂是硫化矿和铜锌碳酸盐矿物、磁铁矿的捕收剂；传统意义上氧化矿捕收剂烷基硫酸、烷基磺酸是典型铜铅锌铁硫化矿和铜铅锌碳酸盐矿物的捕收剂。不同碳链长度黄药的试验证实在同一黄药官能团上,随着烃链长度的增加,药剂的logP值增加药剂的疏水性增加,药剂与矿物作用能的绝对值也略有增加,对铜铅锌铁典型硫化矿和铜铅锌碳酸盐矿物的捕收能力也增加。其中辛基黄药和十二烷基黄药呈现出好的捕收能力。红外光谱检测结果与不限定捕收剂用量的浮选试验结果在总体上有较好的相关关系,但仍然存在部分不一致的情况。1对于铜铅锌铁硫化矿物,凡是红外光谱检测到铜铅锌铁硫化矿物表面存在捕收剂特征吸收峰的捕收剂是可以浮游硫化矿的,但未检测到特征吸收峰的试验药剂,仍然可以浮游硫化矿。2对未活化的3种铜铅锌碳酸盐矿物,红外光谱检测到捕收剂特征吸收峰的捕收剂中较长烃链药剂是可以浮游这些碳酸盐矿物的；但未出现红外光谱捕收剂特征吸收峰的药剂,其中疏水性强的捕收剂仍然可以浮游未活化碳酸盐矿物；对于那些出现红外光谱特征吸收峰的药剂,但可能因为这些药剂的疏水性不够强而不能浮游未活化的碳酸盐矿物；在碳酸盐矿物表面不出现红外光谱特征吸收峰的药剂,其中烃链较短的捕收剂也不能浮游碳酸盐矿物。3对于3种铁氧化矿物,捕收剂与铁氧化矿物作用后出现红外特征吸收峰的可以浮游铁氧化矿物,没有红外特征吸收峰的捕收剂将不能浮游铁氧化矿物。捕收剂-矿物表面相互作用的分子力学模拟和计算结果结合矿物的浮选试验和红外测试结果,同时应用捕收剂的logP值捕收剂的酯水分离系数可以较好地解释捕收剂-矿物表面作用的现象。本文通过分子力学模拟和计算认为捕收剂总体上是以直立式官能团作用与矿物表面的金属原子或者胺捕收剂分子和离子的氢原子与矿物表面的非金属原子作用相互作用,其可能性比以平卧式官能团和碳链与矿物表面共同作用作用于硫化矿表面的可能性大。根据水分子和氢氧根离子与9种试验矿物表面相互作用能而判断出水分子和氢氧根离子是可以在矿物表面形成水化层的；其作用能是捕收剂与矿物表面作用时必须克服的能垒。二硫代类捕收剂黄药、黑药和硫氮类的两个二硫代原子是与黄铜矿表面邻近的铜和铁原子相互作用的。二硫代类捕收剂官能团中只能由一个硫原子与孔雀石和白铅矿表面的一个金属原子相互作用,而不是两个二硫代原子共同与矿物表面两个邻近的金属原子作用。分子力学数据结合药剂的logP值可以较好地解释铜铅锌碳酸盐矿物浮选的规律性,即分子力学数据可以判断捕收剂能否克服矿物表面的水化层而与矿物表面作用,而logP值较大的捕收剂才使矿物表面足够疏水,也就是可以浮游铜铅锌碳酸盐矿物。总体上铜铅锌铁氧化矿与硫化矿相比,捕收剂与氧化矿碳酸盐和氧化物作用能的绝对值降低了,也就是捕收剂与氧化矿碳酸盐和氧化物的作用能力比硫化矿的作用能力减弱了。对铜铅锌碳酸盐矿物的浮选需要加大捕收剂的用量或者增加logP值增加药剂的疏水性才能更好地浮游氧化矿碳酸盐和氧化物分子力学模拟和计算结果指出捕收剂以平卧式官能团和碳链与矿物表面共同作用作用于矿物表面的可能性随着烃链的加长而减小,所有的试验捕收剂中乙基黄药和硫氨酯克服水分子作用层后形成平卧式作用的可能性比较大,其它捕收剂的可能性不大。在黄铜矿表面所有试验捕收剂的这种作用形式是不可能的。论文通过分子力学模拟和计算捕收剂-矿物表面的作用有利于揭示原子层面的浮选基本原理。 【Abstract】 In this paper typical flotation of sulphides chalcopyrite, galena, sphalerite and pyrite,carbonates of Cu/Pb/Zn malachite, cerussite and smithsonite and iron oxides magnetite, hematite and limonite are studied with xanthates ethylxanthate, butylxanthate, octylxanthate and dodecylxanthate, sodium diethyldithiocarbamateDDTC, amonium dibutyldithiophosphteDDTP, lauric amineLA, octodecylamineODA, sodium dodecylsulfateDSF, sodium dodecylsulphonateDSP, oleic acid and isopropyl thionocarbamatePTNC. These minerals, unactivated, interacted with 12 kinds of collectors are detected by FTIR. After reviewing the references, author point out that molecular mechanics could be used in simulating and calculating interaction of Collector-Minerals.The interaction energy of Collector-Minerals are simulated and computed by use of molecular mechanics.According to results of flotation and FTIR, interaction energy of Collector-Minerals can be used in interpreting the mechanism of flotation behavior.After series of flotation tests, there are not strictly traditional sulphide collectors and oxide collectors. Oleic acid is a strong collector of all kinds of tested minerals included sulphides, malachite, smithsonite and iron oxides. The xanthates with long hydrocarbon chain are high efficient cllectors of sulphides, malachite, cerussite and smithsonite. The amine cllectors are also good collectors of sulphides, malachite, cerussite, smithsonite and magnetite. The well known collectors of oxide minerals sodium dodecylsulfate, sodium dodecylsulphonate are also collectors of sulphide minerals and carbonate minerals of Cu/Pb/Zn.The test results of xanthates with different hydrocarbon chain illustrate that xanthatewith the longer of the hydrocarbon chain will show the bigger of reagent logP the stronger of reagent hydrophobic ability, the more negative of interaction energy in Collector-Minerals system slightly, and the stronger of ability to recover typical sulphides and carbonates of Cu/Pb/Zn. The relationship between results of FTIR and flotation results without limit of collector dosage show positive correlative phenomena generally although there are some negative correlative phenomena.1 In sulphide system the collector, which finger mark peak on mineral surface is detected by FTIR, can be used to float sulphides. The collectors, which finger mark peak on mineral surface is not detected by FTIR, can also be used to float sulphides.2 In unactivated carbonates of Cu/Pb/Zn, the collectors with long hydrocarbon chain, which finger mark peak on mineral surface is detected by FTIR, can be used to float carbonates. The collectors with long hydrocarbon chain, which finger mark peak on mineral surface is not detected by FTIR, can also be used to float carbonates. Some of collectors, which finger mark peak on mineral surface is detected by FTIR, can’t be used to float carbonates because of their short hydrocarbon chain.3 In three kinds of iron oxides system, the collectors, which finger mark peak on mineral surface is detected by FTIR, can be used to float these iron minerals, otherwise can not be used to float iron oxide minerals.The results of simulation and computation on interaction energy in Collector-Mineral system can explained the interaction phenomena correctly when it links with flotation results and FTIR results.In this paper it is point out that collector interacts on metal atom on minerals in erect model only polar group interacted on minerals generally, while amine collector interacts on nonmetal atom on minerals in erect model. Its possibility is bigger than that collector interacts on mineral in parallel model polar group and hydrocarbon chain interacted on mineral.According to the interaction energy of H2O and OH- on nine kinds of test minerals, it is concluded that H2O and OH- can interact on minerals and hydrating layer on minerals. Its interaction energy, and so called energy bulwark, must be overcome by collector when collector interacts on minerals.When xanthates, dithiophosphate and dithiocarbamate interact on chalcopyrite, the two S atoms in dithio-group interact on Cu atom and neighbor Fe atom. For example, xanthate, dithiophosphate and dithiocarbamate interact on chalcopyrite in model of the illustrated figure see right When xanthates, dithiophosphate and dithiocarbamate interact on malachite and cerussite, only one of two S atoms in dithio-group interacts on metal atom.Simulation and computation results of molecular mechanics linked with logP data of reagents could be used to explain the mechanism in flotation of carbonates of Cu/Pb/Zn. For example, it is concluded that collectors can or can’t overcome energy bulwark of hydrating layer on minerals according to interaction energy in Collector-Minerals. The collectors, which have big logP, can be used to float carbonate minerals.Comparing with sulphides and oxide minerals carbonates and oxides, interaction energy in Collector-Minerals Carbonates or Oxides system is higher than that in Collector-Sulphides system generally. Therefor it shows that ability of interaction in Collector-Minerals Carbonates or Oxides system is lower than that in Collector-Sulphides system. When unactivated carbonates are flotated totally, collector needs much more dosage or much longer hydrocarbon chain.Simulation and computation results of molecular mechanism also show that the possibility of collectors interacting on minerals is small with long carbon chain when collectors interact on mimerals in parallel model polar group and hydrocarbon chain interacting on minerals. Only ethylxanthate and isopropyl thionocarbamate in test reagents interact on minerals more possibly after overcoming water molecule interaction energy on minerals. All kinds of test collectors are even not able to interact on chalcopyrite in parallel model.This paper shows that molecular mechanics is in favor of opening out foundamental flotation principle in atom scale. 【关键词】 黄铜矿； 方铅矿； 闪锌矿； 黄铁矿； 孔雀石； 白铅矿； 菱锌矿； 氧化铁； 浮选； FTIR； 分子力学； 【Key words】 chalcopyrite； galena； sphalerite； pyrite； malachite； cerussite； smithsonite； oxides of iron； flotation； FTIR； molecular mechanics；